Water-dilutable binder mixtures based on alkyd resins and poly-n-acyl alkyleneimines

ABSTRACT

This invention includes new water-dilutable binder mixtures based on alkyd resins modified by poly{ethylene glycol} and poly{N-acyl alkylene imines}, a process for preparing such binder mixtures, and the use of such binders in oxidatively drying paints and varnishes.

FIELD OF THE INVENTION

This invention relates to new water-dilutable binder mixtures based onalkyd resins and poly-N-acyl alkyleneimines, to processes for theproduction of the new binder mixtures and to their use in oxidativelydrying paints.

STATEMENT OF RELATED ART

In principle, lacquers and paints are divided into physically dryingsystems and chemically drying systems. One form of chemically dryingpaints are oxidatively drying systems in which a crosslinking reactionis initiated by atmospheric oxygen. The most important oxidativelydrying paints now contain binder mixtures based on alkyd resins in whichhighly unsaturated fatty acids are incorporated by condensation in theform of mixed polyesters. Binder mixtures containing so-calledself-emulsifying alkyd resins, i.e. those which, by virtue ofincorporated hydrophilic groups, can be emulsified in water without anyneed for external emulsifiers, are used for water-dilutable paints.Self-emulsifying alkyd resins in which polyethylene glycol isincorporated and of which the residual acid groups have been at leastpartly neutralized by addition of a base are often used as the bindercomponent. The production of aqueous dispersions of such alkyd resins isdescribed, for example, in DE-PS 28 09 840, in DE-PS 15 95 278 and inGerman patent application P 39 32 375.7. These aqueous alkyd resindispersions have excellent stabilities. However, if they are used assole binder component, these alkyd resin dispersions givewater-dilutable paints or coatings which are in need of improvement inregard to their drying properties and in regard to film quality,particularly film hardness.

By contrast, quick-drying films combining high gloss with high hardnessvalues are provided by paints of which the binders are based onpoly-N-acyl alkyleneimines, particularly those according to Germanpatent application P 39 00 859.2. However, most of the poly-N-acylalkyleneimines used there are difficult to emulsify in water. Acceptableemulsifiability in water can only be achieved where poly-N-acylalkyleneimine mixtures containing more than 50% by weight of ethyloxazoline are used. However, a binder mixture of this type givescoatings which are extremely sensitive to water.

DESCRIPTION OF THE INVENTION Object of the Invention

Accordingly, the problem addressed by the present invention was toprovide binder mixtures which would advantageously combine the readyemulsifiability of alkyd resins with the favorable drying properties andfilm quality of poly-N-acyl alkyleneimines and processes for theproduction of such binder mixtures and to enable them to be used inoxidatively drying paints.

SUMMARY OF THE INVENTION

Accordingly, the present invention relates to water-dilutable bindermixtures suitable for oxidatively drying paints based on alkyd resins inwhich polyethylene glycol is incorporated and of which the residual acidgroups have been at least partly neutralized by addition of bases,characterized in that, together with the alkyd resins, they containpoly-N-acyl alkyleneimines prepared by cationic polymerization of one ormore monomers corresponding to general formula I: ##STR1## in which Z isa direct bond or the group >CR⁵ R⁶, where R⁵ and R⁶ may be-the same ordifferent and represent H or alkyl containing up to 2 carbon atoms,

R¹ to R⁴ may be the same or different and represent H, an aromatic oraliphatic radical containing up to 8 carbon atoms, and

R⁷ is an aromatic or aliphatic radical, attached by carbon, containingup to 21 carbon atoms.

The binder mixtures according to the invention are based on alkyd resinswhich have been produced in known manner from monobasic and polybasiccarboxylic acids and/or anhydrides thereof and polyhydric alcohols usingpolyethylene glycol and which have an acid value of 5 to 25.

DESCRIPTION OF PREFERRED EMBODIMENTS

Preferred alkyd resins are the alkyd resins which can be produced inaccordance with German patent application P 39 32 375.7 where particularemphasis is placed on alkyd resins which have been produced from:

the polyhydric alcohols trimethylol propane and penta-erythritol inquantities of 20 to 40% by weight,

fatty acids or fatty acid mixtures in quantities of 20 to 45% by weight;the fatty acids should contain more than 12 carbon atoms and should beat least partly unsaturated,

aromatic monobasic carboxylic acids, such as benzoic acid and/or cyclicderivatives thereof in quantities of up to 25% by weight and

aromatic dicarboxylic acids and/or anhydrides, such as phthalic(anhydride), in quantities of 20 to 35% by weight

using polyethylene glycol having an average molecular weight of 600 to6,000 in quantities of more than 5 and less than 15% by weight (eachcomponent based on the alkyd-resin-forming reactant mixture).

Alkyd resins which have been produced from unsaturated fatty acids, suchas peanut oil, cottonseed oil, soybean and/or sunflower oil fatty acidand/or palmitoleic acid, oleic acid, linoleic acid and/or linolenic acidand/or conjuene fatty acids have proved to be particularly suitable.Other suitable alkyd resins are alkyd resins which have been producedfrom oils, preferably semi-drying or non-drying oils, such as tung oil,castor oil, coconut oil, distel oil, and/or the oils derivable from theabove-mentioned fatty acids.

The alkyd resins preferably used in accordance with the invention havean average molecular weight of 4,000 to 7,000.

The residual acid groups of the alkyd resins are at least partlyneutralized by addition of a base, preferably to degrees ofneutralization of more than 50% and, in particular, completely. Suitablebases are any volatile amines known to the expert, such astriethylamine, 2-amino-2-methylpropan-1-ol and/or ammonia.

The alkyd resins preferably used in accordance with the invention have aresidual acid value below 25, preferably between 5 and 20 and, morepreferably, between 10 and 15, the residual acid value taking intoaccount both free and neutralized residual acid groups.

According to the invention, the binder mixture contains poly-N-acylalkyleneimines produced by cationic polymerization from one or moremonomers corresponding to general formula I: ##STR2## in admixture withand/or bonded to the alkyd resins. In the monomers corresponding togeneral formula I, Z may be a direct bond or may represent the group>CR⁵ R⁶, where R⁵ and R⁶ may be the same or different and represent H oralkyl containing up to 2 carbon atoms. Mixtures of monomerscorresponding to general formula I, in which Z is as defined above, mayalso be polymerized. The mixtures preferably contain monomerscorresponding to general formula I, in which Z is a direct bond, inquantities of more than 50% by weight and, more particularly, inquantities of more than 75 to 100% by weight.

Monomers corresponding to general formula I, in which Z represents thegroup >CR⁵ R⁶, are 6-membered rings which may be regarded as alkylderivatives of the oxazines saturated in the 5,6-position. Monomerscorresponding to general formula I, in which Z is a direct bond, are5-membered rings which may be regarded as alkyl derivatives of theoxazoles saturated in the 4,5-position.

The monomers in question may be produced by typical cyclization orcondensation reactions for cyclic imino-ethers as described, forexample, in DE-PS 1 445 642 or in S. Kobayashi and T. Saegusa inRing-Opening Polymerization, Vol. 2, London 1984, pages 762 et seq.

In the monomers corresponding to general formula I, the substituents R¹to R⁴ may be the same or different and represent hydrogen and/oraliphatic radicals (including by definition the alicyclic compounds)and/or aromatic radicals. The monomers preferably contain hydrogenand/or an aliphatic and/or an alicyclic radical containing up to 8carbon atoms as the substituents R¹ to R⁴. Particularly preferredsubstituents R¹ to R⁴ are hydrogen and aliphatic radicals containing upto 3 carbon atoms. Monomers corresponding to general formula I, in whichat least two of the substituents R¹ to R⁴ are hydrogen, are preferredfor the purposes of the invention.

Monomers in which three of the substituents R¹ to R⁴ represent hydrogenand one of the substituents is an alkyl radical containing up to 3carbon atoms or in which all the substituents R¹ to R⁴ are hydrogen areparticularly suitable. Monomers corresponding to general formula I inwhich Z is a direct bond and the substituents R¹ to R⁴ are hydrogenatoms are most particularly preferred for the purposes of the invention.Monomers such as these are known to the expert as 4,5-dihydrooxazoles orrather 2-oxazolines. The 2-substituted oxazolines in turn may beobtained, for example, from the β-chloroethyl amides or from theethanolamides of the corresponding carboxylic acids or carboxylic acidmixtures by dehydrohalogenation or dehydration.

The definition of the substituent R⁷ derives from the preferred methodof preparation of the monomers corresponding to general formula I, fromcarboxylic acids or carboxylic acid mixtures. Accordingly, thesubstituent R⁷ in the monomers corresponding to general formula I isderived from an aliphatic or aromatic carboxylic acid R⁷ -COOHcontaining up to 22 carbon atoms. In one particular embodiment of theinvention, the poly-N-acyl alkyleneimines are produced by cationicpolymerization of monomers of different structure. Mixtures of monomers,corresponding to general formula I, which differ in the substituent R⁷(R⁷ being derived from aliphatic and aromatic carboxylic acids R⁷ -COOH)are preferably used. In one particularly advantageous embodiment of theinvention, the mixtures of monomers corresponding to general formula Ipartly contain monomers bearing an olefinically unsaturated aliphaticsubstituent in R⁷. This substituent is preferably derived from mono-and/or polyunsaturated fatty acids containing 16 to 22 carbon atoms,such as palmitoleic acid (9c-hexadecenoic acid), petroselic acid(6c-octadecenoic acid), oleic acid (9c-octadecenoic acid), elaidic acid(9t-octadecenoic acid), ricinoleic acid (12-hydroxy-9c-octadecenoicacid), linoleic acid (9c,12coctadecadienoic acid), linolenic acid(9c,12c,15c-octadecatrienoic acid), gadoleic acid (9c-eicosenoic acid),arachidonic acid (5,8,11,14-eicosatetraenoic acid) and erucic acid(13c-docosenoic acid).

For the rest of the monomers corresponding to general formula I, R⁷ is asubstituent derived from aromatic carboxylic acids R⁷ -COOH containingup to 22 carbon atoms. Benzoic acid and/or cyclic derivatives thereofare particularly suitable as the aromatic carboxylic acid.

The mixture of monomers corresponding to general formula I may alsocontain monomers in which the substituent R⁷ is derived from a saturatedcarboxylic acid R⁷ -COOH containing up to 22 carbon atoms. Suitablesaturated carboxylic acids are both the lower carboxylic acids, such asacetic acid, propionic acid and caproic acid, and the higher carboxylicacids, such as lauric acid, palmitic acid, stearic acid, isostearicacid, 2-ethylhexanoic acid, cyclohexane carboxylic acid, myristic acid,and/or behenic acid.

In addition, the aromatic and/or aliphatic carboxylic acids R⁷ -COOH andthe substituents R⁷ derivable therefrom may additionally containsubstituents, like hydroxyl groups, ether groups, ester groups, andhalogens, which do not interfere with polymerization to the poly-N-acylalkyleneimines.

According to the invention, mixtures of monomers corresponding togeneral formula I which contain monomers of which the substituent R⁷ isderived from an unsaturated fatty acid in quantities of 25 to 95% byweight, preferably 50 to 90% by weight and, more preferably, 70 to 90%by weight and monomers of which the substituent R⁷ is derived frombenzoic acid and/or cyclic derivatives thereof in quantities of 5 to 50%by weight and preferably 10 to 30% by weight are preferably used for theproduction of the poly-N-acyl alkyleneimines. In addition, monomerscontaining an alkyl substituent R⁷ derived from a saturated carboxylicacid may be present in quantities of 0 to 25% by weight. All thesepercentages by weight are based on the mixture of monomer reactants.Although larger quantities of the last-mentioned monomers are possible,they adversely affect the drying rate. Mixtures of monomerscorresponding to general formula I which do not contain any monomerswhere the substituent R⁷ is derived from a saturated carboxylic acid areparticularly preferred.

Mixtures of monomers corresponding to general formula I, in which Z is adirect bond and R¹ to R⁴ are hydrogen atoms (the so-called4,5-dihydrooxazoles) and which contain monomers of which the substituentR⁷ is derived from one of the fatty acids mentioned above in quantitiesof 25 to 95% by weight, preferably 50 to 90% by weight and, morepreferably, more than 70% by weight and monomers of which thesubstituent R⁷ is derived from benzoic acid and/or cyclic derivativesthereof in quantities of 5 to 50% by weight and preferably 10 to 30% byweight, are most particularly preferred for the purposes of theinvention.

The cationic polymerization of the monomers corresponding to generalformula I to poly-N-acyl alkyleneimines may be carried out to asubstantially complete conversion. The composition of the poly-N-acylalkyleneimine is determined by the choice of the monomer components. Inthe preferred embodiment of the invention, the poly-N-acylalkyleneimines contain the monomers bearing the various substituents R⁷in substantially statistical distribution.

The polymerization may be initiated by cationic polymerizationinitiators known to one skilled in the art, such astrifluoromethanesulfonic acid methyl ester, boron trifluoride etherate,and/or toluenesulfonic acid methyl ester.

The binder mixtures according to the invention contain alkyd resins inquantities of 10 to 90% by weight and preferably in quantities of 50 to75% by weight and poly-N-acyl alkyleneimines in quantities of 10 to 90%by weight and preferably 25 to 50% by weight. However, it is alsopossible and may be advantageous, depending on requirements, for thebinder mixtures additionally to contain other binders, such aspolyurethanes, polyacrylates, chlorinated rubber, or nitrocellulose. Theother binders may be present in the binder mixtures according to theinvention in addition to the alkyd resin/poly-N-acyl alkyleneiminecombination in maximum mixing ratios of up to 1:1.

The present invention also relates to processes for the production ofthe water-dilutable binder mixtures. According to the invention, twodifferent processes are particularly preferred. In process A, the alkydresins, which contain polyethylene glycol in quantities of less than 15%by weight, based on the alkyd-resin-forming mixture of reactants, andwhich have a residual acid value below 25, are first prepared by methodsknown per se, more particularly by the method according to German patentapplication P 39 32 375.7. The poly-N-acyl alkyleneimines are separatelyprepared by cationic polymerization from the monomers already mentionedby methods known per se, more particularly by the method according toGerman patent application P 39 00 859.2.

The alkyd resins and poly-N-acyl alkyleneimines are then mixed togetherwith intensive stirring at elevated temperature, for example at 100° to175° C. and preferably at temperatures of around 150° C., in mixingratios of alkyd resin to poly-N-acyl alkyleneimine of 10:1 to 1:10,preferably 5:1 to 1:5 and, more preferably, 3:1 to 1:1. Mixing may alsobe carried out in the presence of an organic solvent although this isnot preferred. According to the invention, the binder mixture obtainedafter mixing of the alkyd resins with the poly-N-acyl alkyleneiminespreferably has a residual acid value below 25, preferably in the rangefrom 5 to 20 and, more preferably, in the range from 10 to 15. If thebinder mixture has lower acid values, the mixture is preferablypost-acidified with the dicarboxylic acids and/or anhydrides alreadymentioned with reference to the production of the alkyd resins inaccordance with German patent application P 39 32 375.7, such as forexample maleic anhydride, phthalic anhydride, succinic anhydride. Thebinder mixture is advantageously post-acidified at temperatures of up to150° C. and preferably at temperatures of 100° to 150 ° C. The freehydroxyl groups still present in the alkyd resin presumably form freeacid groups with the preferred anhydrides in the post-acidificationstep. Temperatures considerably higher than 150° C., more particularlytemperatures above 200° C., should be avoided because otherwise the freefatty acid groups formed after post-acidification can react with furtherhydroxyl groups to form higher condensates, which is undesirable.

In principle, the residual acid groups of the alkyd resin may beneutralized before or after mixing of the alkyd resin with thepoly-N-acyl alkyleneimines by addition of the bases already mentioned.Where the binder mixture is post-acidified, it is of advantage toneutralize the residual acid groups in one step afterpost-acidification.

The binder mixture according to the invention can also be prepared bymethod B. In method B according to the invention, the monomerscorresponding to general formula I (oxazines or oxazolines) arepolymerized in the alkyd resin. The polymerization of acrylic acid ormethacrylic acid in an aqueous alkyd resin dispersion is already knownand is described in DE-OS 31 32 937. In contrast to this process, themonomers are directly polymerized in the heated alkyd resin in theprocess according to the invention, for example at temperatures above100° C. up to 200° C. and preferably at temperatures above 130° C. up to170° C., after the addition of typical polymerization initiators. Afterthe preferably complete or substantially complete polymerization of themonomers corresponding to general formula I in the alkyd resin, thebinder mixture obtained shows a distinctly lower acid value than mightbe expected from pure mixing of alkyd resin with poly-N-acylalkyleneimine. The polymerization of the monomers in the alkyd resinapparently uses some of the residual acid groups so that it is logicalto assume that the poly-N-acyl alkyleneimines and/or fragments thereofare grafted onto the alkyd resin in method B. The bonding ratios per sehave not yet been elucidated. At all events, it is of advantage to theemulsifiability of the binder mixture if, after polymerization of themonomers in the alkyd resin, the acid value of the binder mixtureobtained is adjusted to between 10 and 25 by addition of the alreadymentioned dicarboxylic acids and/or anhydrides. Post-acidification iscarried out in the same way as described for method A. After adjustmentof the acid value, the residual acid groups of the binder mixture may beat least partly neutralized by addition of the bases already described,preferably to degrees of neutralization above 50% and, moreparticularly, completely.

According to the invention, both method A and method B are preferablycarried out in the absence of an organic solvent although organicsolvents may be used. Particularly suitable solvents are, above all,high-boiling organic solvents.

The present invention also relates to the use of the binder mixtures foroxidatively drying paints.

To this end, the binder mixtures according to the invention areconverted with a solvent into a binder dispersion. Suitable solvents arewater and/or water-miscible organic solvents, such as acetone and/orbutanone. For environmental reasons, water is preferably used inpredominant quantities and, in particular, exclusively as solvent.

In one particular embodiment, the binder mixtures are first dissolved ina water-miscible organic auxiliary solvent and then dispersed in waterbefore the auxiliary solvent is preferably removed again.

The binder mixture is obtained in the form of a dispersion having abinder solids content of 20 to 60% by weight, preferably 30 to 50% byweight and, more preferably, 35 to 45% by weight.

The dispersion of the binder mixture shows excellent stability instorage and does not coagulate, for example after 3 months attemperatures of 50° C.

The binder mixture is advantageously used as a dispersion in paints inquantities of 15% by weight to 50% by weight and preferably inquantities of 20% by weight to 40% by weight, expressed as solids andbased on paint.

Siccatives, pigments and, optionally, other typical additives may beadded to the dispersion of the binder mixture to form excellentoxidatively drying paints which, despite short drying times, give filmsof high quality and high strength.

Suitable siccatives are any of the compounds known to one skilled in theart which are preferably added in quantities of 0.01 to 1% by weight andmore preferably in quantities of 0.02 to 0.06% by weight, expressed asmetal and based on paint. Smaller quantities than 0.01% by weightsiccatives are also possible, although, under these conditions, paintsgive only slow-drying coatings. The typical additives includeauxiliaries, such as fillers, reactive diluents, antiskinning agents,and/or flow control agents, which are added in the usual quantities forpaints, preferably in quantities of 0 to 60% by weight and, morepreferably, in quantities of 3 to 40% by weight, based on the totalweight of the paint.

EXAMPLES A) Production of a water-dispersible alkyd resin EXAMPLE 1

In a 2 liter three-necked flask equipped with a nitrogen inlet, refluxcondenser, and water separator, 281.0 g of an unsaturated fatty acidmixture (consisting of 6 to 9% by weight of saturated C₁₄₋₁₈ fattyacids, 24 to 28% by weight of oleic acid, 3 to 9% by weight of linoleicacid, and 58 to 62% by weight of a conjugately unsaturated C₁₈ fattyacid mixture (Edenor® UKD 6010)) were heated with stirring for about 3hours to 200° C. with 51.5 g of trimethylol propane, 146.0 g ofpentaerythritol and 224.0 g of p-tert-butyl benzoic acid in the presenceof 100.0 ml of xylene and 2.0 g of a tin-based esterification catalyst(Swedcat™ 3, a product of Swedstab). 41 ml of water was separated ascondensate during the reaction.

After cooling of the reaction mixture, 146 g of pentaerythritol, 336 gof phthalic anhydride, and 106 g of polyethylene glycol having anaverage molecular weight of 3,000 were added and the mixture wasreheated. Another 39 ml of water was separated as condensate.

After an acid value of 11.2 had been reached, the reaction wasterminated and the xylene was subsequently removed in vacuo.

EXAMPLE 2

Example 2 was carried out in the same way as Example 1, except that 280g of a fatty acid mixture containing 8% by weight of saturated C₁₄₋₁₈fatty acids, 28% by weight of oleic acid, 62% by weight of linoleicacid, 1% by weight of a triunsaturated C₁₈ fatty acid and 1% by weightof a >C₁₈ fatty acid (Edenor®SbO₅, a product of Henkel KGaA) was usedinstead of the 281.0 g of the unsaturated fatty acid mixture of Example1.

EXAMPLE 3

Example 3 was carried out in the same way as Example 2 except that 377 gof isophthalic acid were used instead of 336 g of phthalic anhydride.

EXAMPLE 4

Example 4 was carried out in the same way as Example 2 except that thequantity of the unsaturated fatty acid mixture of Example 2 wasincreased from 281 g to 560 g and the quantity of p-tert-butyl benzoicacid added was reduced from 224 g to 46 g.

EXAMPLE 5

Example 5 was carried out in the same way as Example 1 except that 281 gof a fatty acid mixture containing 10 % by weight of saturated C₁₂₋₁₆fatty acids, 5% by of palmitoleic acid, 1% by weight of margaric acid,2% by weight of stearic acid, 67% by weight of oleic acid, 12% by weightof linoleic acid, 1% by weight of linolenic acid and 2% by weight of>C₁₈ fatty acids (Edenor®FTiO₅, a product of Henkel KGaA) were usedinstead of the 281.0 g of the unsaturated fatty acid mixture of Example1.

B) Production of the polyoxazolines

Oxazolines substituted in the 2-position which had been produced mainlyfrom carboxylic acids or carboxylic acid methyl esters via thehydroxyethyl amides by dehydrating cyclization in accordance withearlier application EP 88 118 090.5 were used as starting materials.Even where they had been produced from carboxylic acid mixtures ormethyl esters of carboxylic acid mixtures, the oxazolines were notsubjected to fractional distillation, so that the substituents R in theoxazolines substantially corresponded in their composition to thecompositions in the carboxylic acid or methyl ester mixtures(determination by capillary gas chromatography). Carboxylic acids ormethyl esters were generally used in technical purity. The compositionof the oxazolines used based on fatty acid mixtures (or methyl estermixtures) of natural origin is shown in Table 1. The 2-oxazolinesaryl-substituted in the 2-position, such as 2-phenyl-2-oxazoline, wereproduced by the process according to DE 39 14 133.

EXAMPLE 6

In a 1 liter three-necked flask equipped with a stirrer and refluxcondenser, 380 g (1.25 mole) of oxazoline based on soybean oil fattyacid and 120 g (0.82 mole) of oxazoline based on benzoic acid wereheated under nitrogen together with 2.4 g of trifluoromethane sulfonicacid methyl ester and stirred for 1 hour at 160° C. The polymersolidified on cooling to room temperature.

EXAMPLE 7

121.6 g of oxazoline based on soybean oil fatty acid and 14.7 g ofoxazoline based on benzoic acid were polymerized as in Example 6 byaddition of 0.65 g of trifluoromethyl sulfonic acid methyl ester.

                  TABLE 1                                                         ______________________________________                                        Oxazoline                                                                     produced   Content of oxazolines                                              from       Based on          % by weight                                      ______________________________________                                        Soybean oil                                                                              Saturated C.sub.16-20 fatty acids                                                               17                                               fatty acid Oleic acid        26                                               (Edenor ® Sj,                                                                        Linoleic acid     50                                               Henkel)    Linolenic acid    7                                                Ricinoleic Palmitic acid     2                                                acid       Stearic acid      1                                                (Edenor ® Ri                                                                         Oleic acid        5                                                90, Henkel)                                                                              Ricinoleic acid   88                                                          Linoleic acid     4                                                ______________________________________                                    

EXAMPLE 8

60.8 g of oxazoline based on soybean oil fatty acid and 32.1 g ofoxazoline based on ricinoleic acid and also 29.4 g of oxazoline based onbenzoic acid were polymerized as in Example 6 by addition of 0.6 g oftrifluoromethane sulfonic acid methyl ester.

C) Dispersion EXAMPLE 9

100 g of the alkyd resin of Example 2 together with 100 g of thepolyoxazoline of Example 6 were dissolved with stirring in 150 g ofbutanone. 2.7 g of triethyl amine was added to the clear solutionobtained. 300 g of deionized water was then added with stirring, afterwhich the butanone was removed by distillation. A fine-particle stableemulsion having a polymer solids content of 40% by weight was obtained.

D) Polymerization of the oxazolines in the alkyd resin EXAMPLE 10

In a 2 liter three-necked flask equipped with a stirrer and refluxcondenser, 500 g of the alkyd resin of Example 2 were heated undernitrogen to 120° C. together with 378 g of oxazoline based on soybeanoil fatty acid and 122 g of oxazoline based on benzoic acid. After theaddition of 2.8 g of trifluoromethane sulfonic acid methyl ester, thetemperature was increased to 160° C. and the reaction mixture wasstirred for 1 hour at that temperature.

After cooling under nitrogen to room temperature, 24.7 g of solid maleicanhydride was added. The reaction mixture was then reheated to 150° C.and stirred for another hour.

A resin having an acid value of 15 was obtained. This resin wasdissolved in butanone as in Example 9 and, after the addition oftriethyl amine, the resulting solution was dispersed in water.

E) Production of a clear lacquer EXAMPLE 11

0.15 g of a siccative (Servosyn™ WEB, Co siccative) containing 8% byweight of cobalt and 0.50 g of a siccative (Servosym WEM, Zr siccative)containing 12% by weight of zirconium were added with stirring to 100 gof the dispersion prepared by method C or method D.

A clear lacquer was obtained and was applied by knife-coating with a gapwidth of 100 μ.

The Konig pendulum hardnesses (DIN 53 157) of the clear lacquers basedon various dispersions produced in accordance with Example 11 are shownin the following:

clear lacquer based on dispersions produced in accordance with Example 9from equal quantities by weight of the alkyd resin of Example 2 and thepolyoxazoline of Example 6: 1 day 23"; 7 days 46"; 14 days 63"; 50 days105";

clear lacquer based on dispersions produced in accordance with Example 9from equal quantities by weight of the alkyd resin of Example 3 and thepolyoxazoline of Example 6:

1 day 28"; 7 days 49"; 14 days 69"; 50 days 112";

clear lacquer based on dispersions produced in accordance with Example10: 1 day 22"; 7 days 34"; 14 days 61"; 50 days 100".

The invention claimed is:
 1. Water-dilutable binder mixtures that aresuitable for oxidatively drying paints, said binder mixtures comprisingalkyd resins in which polyethylene glycol is incorporated and of whichthe residual acid groups have been at least partly neutralized byaddition of bases, wherein the improvement comprises the presence in thebinder mixtures of poly-N-acyl alkyleneimines prepared by cationicpolymerization of at least two chemically distinct types of monomerscorresponding to general formula I: ##STR3## in which Z is a direct bondor the group ##STR4## where R⁵ and R⁶ may be the same or different andrepresent H or alkyl containing up to 2 carbon atoms,R¹ to R⁴ may be thesame or different and represent H, or an aromatic radical or aliphaticradical, each containing up to 8 carbon atoms, and R⁷ is an aromatic oraliphatic radical, attached by carbon, containing up to 21 carbonatoms,wherein from 5 to 50% by weight of the monomers corresponding togeneral formula I have an aromatic radical as R⁷, from 25 to 95% byweight of the monomers corresponding to general formula I have anolefinically unsaturated radical as R⁷, and not more than 25% by weightof the monomers corresponding to general formula I have a saturatedalkyl group as R⁷.
 2. Binder mixtures as claimed in claim 1, wherein thepoly-N-acyl alkyleneimines present in the binder mixtures have beenproduced from monomers corresponding to general formula I in which allthe substituents R¹ to R⁴ are hydrogen atoms and Z is a direct bond. 3.Binder mixtures as claimed in claim 2, which contain poly-N-acylalkyleneimines which have been produced by polymerization of a mixtureof monomers comprising from 10 to 30% by weight of monomers with anaromatic moiety in R⁷ and from 50 to 90% by weight of monomers with anolefinically unsaturated moiety in R⁷, and, optionally up to 25% byweight of monomers with a saturated alkyl group as R⁷.
 4. Bindermixtures as claimed in claim 3, wherein the alkyd resin component hasbeen produced by reacting monobasic and polybasic carboxylic acids,anhydrides thereof, or mixtures of acids and anhydrides with polyhydricalcohols including polyethylene glycol in quantities below 15% byweight, based on the mixture of alkyd-resin-forming reactants.
 5. Bindermixtures as claimed in claim 4, wherein more than 50% of the residualacid groups of the alkyd resins are neutralized and the alkyd resinshave a residual acid value above 5 and below 20, expressed as free andneutralized carboxylic acid groups.
 6. Binder mixtures as claimed inclaim 5, wherein the residual acid groups of the alkyd resins are atleast partly neutralized with volatile amines, ammonia, or a mixture ofammonia and at least one volatile amine.
 7. Binder mixtures as claimedin claim 6, comprising alkyd resins in quantities of 50 to 75% by weightin admixture with, bonded to, or both in admixture with and bonded to,poly-N-acyl alkyleneimines in quantities of 25 to 50% by weight, basedon the binder mixture.
 8. A process for the production of the bindermixtures claimed in claim 1, wherein the monomers corresponding togeneral formula I are polymerized in alkyd resin to form poly-N-acylalkyleneimines, and, optionally, the reaction mixture obtained afterpolymerization of the monomers in the alkyd resin is reacted withdicarboxylic acids, anhydrides thereof, or a mixture of any two or moredicarboxylic acids and/or anhydrides of dicarboxylic acids.
 9. A paintcomprising binders as claimed in claim 7 in quantities of 20% by weightto 40% by weight, expressed as solids and based on paint.
 10. Bindermixtures as claimed in claim 1, wherein the poly-N-acyl alkyleneiminespresent in the binder mixtures have been produced from monomerscorresponding to general formula I in which the substituents R¹ to R⁴may be the same or different and represent H or alkyl radicalscontaining up to 3 carbon atoms, at least two of the substituents beinghydrogen atoms.
 11. Binder mixtures as claimed in claim 1, wherein thealkyd resin component has been produced by reacting monobasic andpolybasic carboxylic acids, anhydrides thereof, or mixtures of acids andanhydrides with polyhydric alcohols including polyethylene glycol inquantities below 15% by weight, based on the mixture ofalkyd-resin-forming reactants.
 12. Binder mixtures as claimed in claim1, wherein more than 50% of the residual acid groups of the alkyd resinsare neutralized and the alkyd resins have a residual acid value above 5and below 25, expressed as free and neutralized carboxylic acid groups.13. Binder mixtures as claimed in claim 1, wherein the residual acidgroups of the alkyd resins are at least partly neutralized with volatilebases.
 14. Binder mixtures as claimed in claim 1, comprising alkydresins in quantities of 10 to 90% by weight in admixture with, bondedto, or both in admixture with and bonded to, poly-N-acyl alkyleneiminesin quantities of 10 to 90% by weight, based on the binder mixture.
 15. Apaint comprising binders as claimed in claim 1 in quantities of 20% byweight to 40% by weight, expressed as solids and based on paint.
 16. Apaint comprising binders as claimed in claim 6 in quantities of 20% byweight to 40% by weight, expressed as solids and based on paint.
 17. Apaint comprising binders as claimed in claim 5 in quantities of 20% byweight to 40% by weight, expressed as solids and based on paint.
 18. Apaint comprising binders as claimed in claim 2 in quantities of 15% byweight to 50% by weight, expressed as solids and based on paint.
 19. Apaint comprising binders as claimed in claim 1 in quantities of 15% byweight to 50% by weight, expressed as solids and based on paint.